Softener and mold inhibitor for baked products



nited States Patent O ice 3,435,639 SOFTENER AND MOLD ITOR FOR BAKEDPRODUCTS Int. Cl. AZld /00 US. Cl. 99-91 6 Claims ABSTRACT OF THEDISCLOSURE A composition useful as a softener and mold inhibitor inbaked products comprising a blend of a low iodine value monoglycerideand a lower monocarboxylic acid ester of a polyhydric alcohol.

This application is a division of the application of William H.Knightly, Ser. No. 385,030, filed July 24, 1964, now matured into U.S.Patent No. 3,369,907, issued Feb. 20, 1968.

This invention relates to a composition of matter which is useful as asoftener and mold inhibitor in baked products. In particular, thisinvention relates to using a blend of a normally hard, low iodine valuemonoglyceride and a lower monocarboxylic acid ester of a polyhydricalcohol as a softener and mold inhibitor in baked products.

It is current practice in the baking industry to use monoanddiglycerides to retard the rate of crumb firming, and sodium or calciumpropionate to inhibit the rate of mold growth. This makes it necessaryfor the bakeries to store two materials and to handle and measure twomaterials during the baking operation.

In the preparation of baked products, it is often difficult tocompletely disperse the monoand diglyceride softening agents into thedough or batter for the mixing time is limited to a few minutes and noheat is applied sufficient to melt hard glycerides. Therefore, themonoand diglycerides which are used as softening agents are usually softpastes or plastic materials which generally means that they haverelatively high iodine values.

The calcium or sodium propionates, which are used as mold inhibitors,are very effective in retarding the growth of mold but also adverselyaffect the functioning of the yeast in yeast-leavened baked products.These propionate salts greatly increase proof time and may alsoadversely affect the grain and volume of the resulting product.

It is an object of this invention to provide a composition which is aneffective softener and mold inhibitor for baked products.

Another object of the invention is to provide a composition containing alow iodine value monoglyceride which is readily dispersed in the doughor batter of baked products.

An additional object is to provide a mold inhibitor for yeast-leavenedbaked products which does not adversely affect proof time.

Other objects and purposes of this invention will be apparent to thoseskilled in the art in view of the description which follows.

It has been discovered that a composition consisting essentially of anormally hard, low iodine value monoglyceride having an average iodinevalue in the range of about 6 to about 45 and a lower monocarboxylicacid ester of a polyhydric alcohol having from 2 to 6 hydroxyl groups isan effective softening agent and mold inhibitor for baked products. Thisis a significant improvement in 3,485,639 Patented Dec. 23, 1969 the artof making baked products, for one product now performs the functionswhich formerly required two products. The resulting saving in storing,handling and measuring one product rather than two is substantial. Inaddition, there is no problem of dusting associated with thesecompositions.

Several attempts were made at formulating compounds and compositions tofunction as combined softeners and mold inhibitors. All of the earlyattempts resulted in products which were either not as effecitve ascurrently used softening agents and/or did not give sufficientprotection against the development of mold. Finally it was found thatnormally hard, low iodine value monoglycerides are exceptionallyeffective softening agents for baked products. But this presented theproblem of incorporating the monoglyceride into the dough or batter, forlow iodine value monoglycerides are generally hard materials which arenot readily dispersed in dough or batter. This problem is accentuated bythe fact that the time for mixing the dough or batter may be limited toa few minutes and there is no heat applied sufficient to melt hardglycerides, for it is well known that overmixing tends to have anadverse effect on the resulting baked product.

In accordance with this invention, a normally hard, low iodine valuemonoglyceride having an average iodine value in the range of about 6 toabout 45 is blended with a lower monocarboxylic acid ester of apolyhydric alcohol having from 2 to 6 hydroxyl groups to yield a softpaste or plastic material which is readily dispersed in dough or batter.It should be noted that a monoglyceride prepared from a monocarboxylicacid of about 12 carbon atoms (lauric acid) or its equivalent may have alow iodine number and still be a soft paste or plastic material. As usedin this specification and the claims which follow, the term normallyhard, low iodine value monoglyceride is meant to include monoglyceridesprepared from monocarboxylic acids containing at least 12 carbon atomsper molecule, and therefore includes laurates which may be plasticmaterials. Monoglycerides prepared from lauric acid having iodine valuesof about 6 to about 10 may be sufficiently dispersible as to be usefulin accordance with this invention, but in general, the minimum iodinevalue should be about 15.

Generally, as the carbon atom content of the monocarboxylic acid used toprepare the low iodine value monoglyceride increases, the monoglyceridebecomes a harder material, and in order to obtain ready dispersibility,the minimum iodine value should be higher. Of course, more of the lowermonocarboxylic acid ester may be blended with the normally hard, lowiodine value monoglyceride to render it more dispersible, but thisreduces the effectiveness of the blend as a softener. It is particularlypreferred to use normally hard, low iodine value monoglycerides preparedfrom monocarboxylic acids containing from about 16 to about 20 carbonatoms per molecule for these monoglycerides are particularly effectivesofteners. When using these preferred monoglycerides, they should haveiodine values ranging from about 20 to about 36 in order to insure theirdispersibility in dough or batter.

Of particular importance is the fact that the compositions of thisinvention are as effective or more effective than currently usedsoftening agents, and in addition, they function as mold inhibitors.With respect to mold inhibition, the compositions of this invention areeffective mold inhibitors without adversely affecting proof time or thevolume and grain of the resulting baked product.

The normally hard, low iodine value monoglycerides, which term is meantto include mixtures of mono-, diand/ or triglycerides, which are usefulin the compositions of this invention are those having an average iodinevalue in the range of about 6 to about 45, with an iodine value of about20 to about 36 being particularly preferred. It is within the scope ofthis invention to use monoglycerides having iodine values outside ofthis range by blending them with a monoglyceride having an iodine valuesufficient to form a monoglyccride mixture having an iodine value withinthe stated range. If the normally hard, low iodine value monoglyceridecomponent of the compositions of this invention has an iodine value lessthan about 6, it is necessary to add more lower monocarboxylic acidester to render the composition sufiiciently plastic than is Thenormally hard, low iodine value monoglyceridelower monocarboxylic acidester of a polyhydric alcohol composition may be prepared by melting thenormally hard, low iodine value monoglyceride and then incorporating thelower monocarboxylic acid ester in the melt. Thereafter, the melt may bemixed thoroughly on a Votator to form a uniform mixture and then cooledto form a plastic, readily dispersible composition. If more than onenormally hard, low iodine value monoglyceride or monoglyceride mixtureis to be used, one of the monorequired for effective mold inhibition andthe effectiveglycerides may be melted and the other monoglycerides nessof the blend as a softener is imparied. On the other and the lowermonocarboxylic acid ester added to the melt hand, if the iodine value ofthe glyceride is more than in any order, so long as the temperature ofthe melt is about 45, the softening properties of the blendedcomsufiicient to melt all of the added components.

position will not be as eifective as currently used soften- 1 Thecompositions of the present invention are usually ing agents. It hasbeen found that monoglycerides or incorporated into baked products inamounts which are monoglyceride mixtures having average iodine values inufficient effectively to inhibit the growth of mold durthe range of fromabout to about 36 are particularly ing storage for durations of about aWeek and also sufiieifective softening agents and can be renderedsufiiciently cient to preserve the softness of the product duringstorplastic by the amount of lower monocarboxylic acid ester 20 age. Ingeneral, amounts of the lower monocarboxylic required for effective moldinhibition. acid ester as little as about 0.04% based on the weight ofThe lower monocarboxylic acid esters of a polyhydric the flour containedin the product are sufiicient for efiecalcohol having from 2 to 6hydroxyl groups which are tive mold growth inhibition in the product.Since greater useful in the compositions and method of this inventionamounts of the compositions of the present invention are are effectivemold inhibitors and softening agents. Since required to impart thedesired softening or anti-staling these compounds are to be incorporatedinto baked prodcharacteristics to the baked product, the criticalconcenucts which are to be ingested, it is essential that they betrations of the said composition in the baked product are edible. Thepolyhydric alcohol may be completely esteriaccordingly determined by theamounts required for fied or partial esters may also be used.Conventional that purpose. In general, in yeast-leavened products, fromesterification procedures may be used to prepare these about 0.2% toabout 1.0% of the composition based esters. Typical of the polyhydricalcohols which may be upon the weight of the flour in the product issufiicient used are propylene glycol, dipropylene glycol, glycerol, toimpart both mold growth inhibition and softness or erythritol,pentaerythritol, arabitol, xylitol, sorbitol, anti-staling properties tothe baked product; in baked manntol, and cyclic inner ethers ofpolyhydric alcohols products which do not contain yeast, however, thecomhaving at least 2 hydroxyl groups such as isosorbide, sorpositions ofthe present invention are usually used in bitan, isomannide andmannitan. amounts within a range of about 0.8% to about 20.0%

The lower monocarboxylic acids which may be used to based upon theweight of the flour in the baked product. esterify the polyhydricalcohol are the monocarboxylic The following examples illustrate thepreparation of acids having from 2 to 7 carbon atoms. Examples of lowermonocarboxylic acid esters of polyhydric alcohols monocarboxylic acidswhich may be used are acetic, proof from 2 to 6 hydroxyl groups, theformation of blends pionic, butyric, valeric, caproic, sorbic andbenzoic. Proof lower monocarboxylic acid esters with normally hard,pionic acid has been found to be particularly effective. In low iodinevalue monoglycerides and the preparation of addition to using the acids,their equivalent anhydrides, baked products. halides and esters may alsobe used to prepare the esters EXAMPLE I of polyhydric alcohols.

In general, the lower monocarboxylic acid esters of a Preparauon ofproplonate esters of glycerin polyhydric alcohol having from 2 to 6hydroxyl groups About 460 Of glycerin moles) were Placed in a should beblended with the low iodine value monoglycer- 3-heeked flask q p with amechanical stiffer, e011- ide in amounts sufiicient to render themixture a soft paste dehsel', thermometer and pp fuhhel- 1250 or plasticmaterial. The blend must be soft enough to be moles) of Propiehieahhydfide was added dfepwise at a thoroughly dispersed in the dough atroom temperature. temperature of Over a Period of 225 hours- The amountof lower monocarboxylic acid ester required The reaction mixtul e washeated for 3 hours at will vary depending upon the hardness of themonoglycaftel' the Prepiohie ahhydride had been addederide and theparticular ester which is used. Usually Piehie acid was stripped 05under reduced Pressure, and more ester is required as the iodine valueof the monoglyca: the resulting miXtllfe was distilled v a 10 inch eridedecreases and the molecular weight of the lower VigfeallX 6011111111 Thefchewing four liquid cuts were monocarboxylic acid ester increases. Ithas been found collected:

Pot Vap Sap. No OH No Acid No cdllhil 110-115 98-100 542 29s. 5 7. 45176 g, 2 116 107 548 274 1. 07 14. 1 114-121 105-110 561 244 0. 65 243:5. 4 117-120 105-110 570 0. 30 360 33, 1 Residue 561 158 0. 66 40 4, 2

that blends containing from about 20 to about 75 weight 70 Theapproximate composition of each fraction was percent of lowermonocarboxylic acid ester are generally as fOllOWSI soft enough to bedispersed in the dough. If more than about 75 weight percent of thelower monocarboxylic acid g g gg iig dlproplonate' ester is present, theblend will not be as effective as cur- 1 a renfly used softening agentsat comparable s. 75 cit 2% mono and tri and 98%; dipropionate.

Cut #4-70% diand 30% tripropionate.

EXAMPLE II Preparation of isosorbide dipropionate A three-liter,3-necked flask equipped with a stirrer, thermometer, dropping funnel anda reflux condenser was charged with 438.3 g. (3 moles) of isosorbide and2 g. of p-toluenesulfonic acid. The isosorbide was heated to 80 C., andthen 858 g. (6 moles plus excess) of propionic anhydride were addeddropwise with stirring over a 90 minute period. The temperature duringthe addition varied between 80-90 C. Thereafter, the reaction mixtureWas heated for 10 hours at 100 C. and then for 4 hours at 155-160 C.,after which propionic acid and excess propionic anhydride were strippedoff under vacuum.

The resulting liquid product was treated with 10 g. of activated carbonand distilled through a 10 inch vigreaux column at 135-138 C. and 0.5mm. pressure. 540 g. of isosorbide dipropionate having a SaponificationNo. of 432, OH No. 0.38 and Acid No. of 0.37 was obtained.

EXAMPLE III Formation of a blend of a normally hard, low iodine valuemonoglyceride and a glyceryl propionate Blends of normally hard, lowiodine value monoglycerides blended with glyceryl dipropionate andglyceryl tripropionate were prepared. A monoand diglyceride mixturehaving an iodine value of about 2 Was heated to a temperature of about150 F. After a melt was formed, another monoand diglyceride mixturehaving an iodine value of about 36 was added to the melt. After bothmonoglyceride mixtures were completely melted, they were separated intotwo portions and glyceryl dipropionate was added to one portion andglyceryl tripropionate to the other. Then each portion was votated andcooled to form a plastic composition. The Weight ratios of thecomponents of the two compositions was as follows:

Composition A: Parts by weight Dough: Percent (flour as 100%) FlourSugar 8 Salt 2 Lard 3 Milk powder 6 Water 1 Variable Softener and moldinhibitor 0.50

1 57% of the total water was added to the sponge and 43% was added tothe dough. The total amount of Water used varied depending upon theflour absorption properties. The amount of water required was determinedby a farinograph method which is described in Cereal Laboratory Methodscom piled by the American Association of Cereal Chemists, 6th edition,pp. 132-139.

The sponges were prepared by dissolving the yeast in a portion of thewater, and this composition was added to a mixer along with flour, yeastfood and the balance of the Water. These ingredients were mixed forabout 3 minutes and thereafter fermented for about 4.5 hours.

The fermented sponges were returned to the mixer and all of the doughingredients were added. The doughsponge mixtures were mixed to fulldevelopment (usual 1y about 11 to 13 minutes), fermented for 20 minutes,divided, allowed a 10 minute proof, sheeted, molded, sealed and placedinto bread pans. Then the dough was proofed at about 100 F. and 85relative humidity in the usual manner to template height and baked forabout 20 minutes at 425 F.

Prior to baking, the bread dough was evaluated for dough conditioningproperties and proof time. After baking, the bread was evaluated forvolume, grain, softness and mold inhibition. Softness studies onhalf-inch thick bread slices were carried out over a period of 6 daysusing a gelometer to determine softness. The gelometer value representsthe number of grams of shot required to depress the gelometer plunger agiven distance (4 mm. in these evaluations) into the bread slice. Themold inhibition test comprised exposing the loaves of bread to roomconditions and then storing them at 100 F. and 85% relative humidity.

Compositions A and B of Example 111 were evaluated Monoand diglyceridemixture (I.V. 36) 38 as softeners and mold inhibitors and were comparedto Monoand diglycen'de mixture (I.V. 2) 22 a standard which contained0.15% calcium propionate as Glyceryl dipropionate a preservative. Thefollowing results were obtained:

Gelometer Proof Volume (cc.) values (avg.) Softener and mold Dough timeGrain Mold inhiinhibitor conditioning (min) A B C D Avg. 3 days 6 days 6days bition (days) Standard Very good 73 2,535 2, 460 2,575 2,605 2, 544326 400 Good 13 (no softener). CompositionA do 7 2,650 2,535 2,550 2,7502,621 279 328 Good 13 CompositionB do 68 2,655 2,575 2,605 2,600 2,609268 327 Good 13 Composition B: Parts by weight Monoand diglyceridemixture (I.V. 36) 38 These results indicate that both Compositions A andB M and dlglycel'lde InlXtllfe 2 were effective bread softeners and moldinhibitors. Glyceryl trtpropionate 40 As used in the claims whichfollow, the term consist- The blend of the two monoglyceride mixturesused in Compositions A and B had an average iodine value of 23.5.

EXAMPLE IV Preparation of bread using softening agentmold inhibitorcompositions The following bread formula and procedures were used toevaluate Compositions A and B of Example III as bread softeners and moldinhibitors according to the sponge-dough method:

ing essentially of includes compositions containing the namedingredients and any other ingredients which do not deleteriosuly affectthe compositions for the purposes stated in the specification.

Having completely described this invention, what is claimed is:

1. An antistalant and antimycotic composition for use in yeast-raisedbaked goods consisting essentially of a blend of a normally hard, lowiodine value monoglyceride having at least 12 carbon atoms per moleculeand an average iodine value in the range of about 6 to about 45 and anester of a lower monocarboxylic acid and a polyhydric alcohol havingfrom 2 to 6 hydroxy groups, said lower monocarboxylic acid ester beingpresent in amounts ranging from about 20 to about 75 weight percent ofthe total composition.

7 s 2. The composition of claim 1 in which the lower References Citedmonocarboxyhc ac1d ester is a propionate. UNITED STATES PATENTS 3. Thecomposition of claim 2 in which the lower monocarboxylic acid ester is aglyceryl propionate 2,764,605 9/ 1955 Embree et 99-118 XR 4. Thecomposition of claim 3 in which the normally 6,41 1 960 Weiss 99118hard, low iodine value monoglyceride has an average 3, 57,213 6/1966Colby 99-94 iodine value in the range of about 20 to about 36. M

5. The composition of claim 4 in which the lower RAYMOND N. JONES,Primary Examiner monocarboxylic acid ester is a glyceryl dipropionate.

6. The composition of claim 4 in which the lower 10 US. Cl. X.R.monocarboxylic acid ester is a glyceryl tripropionate. 99-150, 222

